Process for removing contaminants from polyolefins

ABSTRACT

Polyester and cellulosic contaminants are removed from the surfaces of polyolefins by contacting the polyolefins with an aqueous composition of alkali metal hydroxide and/or alkaline earth metal hydroxide; and with an oxidizing agent.

TECHNICAL FIELD

The present invention is concerned with removing certain contaminantsfrom polyolefins and especially concerned with removing polyester andcellulosic contaminants including cotton and paper from the polyolefin.The decontamination process of the present invention can be carried outwithout employing organic solvents. The process of the present inventionis accomplished without degradation of the treated polymer to anysignificant degree.

BACKGROUND ART

Polyolefins and particularly polymonoolefins such as polypropylene areused as bale wrapper, for example, for baling cotton fibers andpolyester fibers. In order to recycle the polyolefins such must beadequately cleaned, which includes removing certain contaminantsincluding polyesters and cellulosic materials such as cotton and paper.Sometimes, low levels of such contaminants may be removed during meltprocessing by screen packs positioned at the end of an extruder barrel.However, in these bale-wrappers, the presence of both polyester andcellulosic (cotton and paper fibers) creates a unique problem. Thecellulosic fibers degrade at temperatures required to melt-processpolyesters and at lower temperatures the cellulosic and polyester fiberscause plugging of the filter screens used in extruding the recycledpolymer. Mechanical methods that have been attempted have failed to givegood separations. In addition, washing with water, with or withoutdetergent, is not a satisfactory approach. Furthermore, difficultieshave been encountered in achieving a satisfactory process since thecustomers for reprocessable, reusable polyolefins have highspecifications that are close to those for the original polyolefinmaterial.

SUMMARY OF INVENTION

The present invention is concerned with a process for removing polyesterand cellulosic contaminants from polyolefins. The process of the presentinvention provides for the degradation of polyester and cellulosiccontaminants without adversely effecting the properties of thepolyolefins. Moreover, the degraded materials are readily removable fromthe polyolefin. The process of the present invention preferably employsaqueous compositions and does not require the use of organic solvents.The chemicals employed pursuant to the present invention arecommercially available, relatively inexpensive, reasonably safe tohandle, safe to mix, and water soluble.

More particularly, the process of the present invention comprisescontacting a polyolefin contaminated with polyester and cellulosiccontaminants with an aqueous composition of an alkali metal hydroxideand/or alkaline earth metal hydroxide; and with an oxidizing agent tothereby degrade the polyester and cellulosic contaminants. The treatedpolyolefins obtained by the present invention can be melt reprocessed inan economical manner to provide fibers. The recycled fibers exhibit anacceptable level of mechanical properties.

BEST AND VARIOUS MODES FOR CARRYING OUT INVENTION

The contaminated polyolefins treated pursuant to the present inventionare not degraded by the chemicals employed to degrade the polyester andcellulosic contaminates. The polyolefins treated pursuant to the presentinvention include polymers of olefins, and particularly homopolymers ofmonoolefins such as polyethylene, polypropylene, polyisobutylene,polybuten-1 and polystyrene and preferably polypropylene and copolymersof two or more monoolefins with each other such as copolymers ofethylene with propylene. The polyolefins thus treated may be formed intofibers, films or other molded products. Both amorphous and crystallinepolymers can be treated pursuant to the present invention.

In a typical example, polypropylene bale-wrappers are processed forrecycling to form recycled polypropylene fibers.

Used polypropylene bale-wrappers for bales of cotton and polyesterfibers after use are typically contaminated with the followingcontaminants:

1 to 2% cotton

1 to 2% polyester

1 to 2% paper (e.g., labels and tags)

<1% metal (e.g., wires, clips, and staples)

<1% wood

<1% dirt

<1% grease and oil

Dirt and grease may be removed by conventional washing, and metals areremoved by mechanical processes as suggested in the prior art.

Pursuant to the present invention, the polyester fibers, such aspolyethylene terephthalates (e.g. dacron), and cellulosic contaminantssuch as the cotton fibers and paper (e.g.--paper labels) are removedthereby preventing these contaminants from finding their way to theextruder and creating problems. The problem lies with the customerspecification that a 250-mesh-filter screen be used in the extrusionprocess. It is extremely easy for the cellulosic and polyester fibers,if present, to plug such a fine-mesh-filter screen at thepolypropylene-processing temperature. Thus, a lot of shut-down time isexperienced and the process becomes uneconomical. In addition, smallfibers in the final product can adversely effect properties. The papercontaminants in many instances include adhesive coatings such aspolyvinylacetate which arc also removed pursuant to the presentinvention.

It is essential in order to achieve the results desired by the presentinvention to contact the contaminated polyolefin with both a hydroxidecomposition and with an oxidizing agent. The hydroxide composition istypically an aqueous solution of an alkali metal hydroxide and/oralkaline earth metal hydroxide. Examples of such are sodium hydroxide,potassium hydroxide, and calcium hydroxide. The preferred hydroxideemployed pursuant to the present invention is sodium hydroxide. Theaqueous hydroxide solutions typically contain about 5 to about 50% byweight of the hydroxide, preferably about 10 to about 30% by weight ofthe hydroxide, and most preferably about 20% by weight.

The oxidizing agent is preferably, but not necessarily, employed as anaqueous composition. Suitable oxidants include alkali metalhypochlorites such as sodium hypochlorite, and sodium peroxide. Aqueouscompositions of the oxidizing agent typically contain about 0.01% toabout 10%, preferably about 0.1 to about 1% by weight and mostpreferably 0.12 to about 0.15 weight % of the oxidizing agent. Thehydroxide and oxidizing agent can be employed as separate compositionsand used to treat the polyolefin simultaneously or in any sequence.However, according to preferred aspects of the present invention, boththe hydroxide and oxidizing agent are included in the same aqueouscomposition to treat the polyolefin. For instance, the hydroxide tendsto stabilize the oxidizing agents such as the sodium hypochlorite whichcan be somewhat difficult or dangerous to handle in a composition thatbecomes acidic. As the sodium hypochlorite is utilized, acid is formed.However, in the presence of the hydroxide, such acid is neutralized bythe hydroxide thereby stabilizing the composition. In addition, thehypochlorite tends to react with metals that might be present ascontaminants from wires, clips and staples that might have been used.However, the presence of the hydroxide tends to noticeably retard such areaction thereby leaving the hypochlorite available for degradation ofthe cellulosic materials.

It is essential pursuant to the present invention, as stated above, thatboth the hydroxide and oxidizing agent be employed. In particular, thehydroxide tends to degrade the polyester but not the cellulosicmaterials. An additional advantage is that the caustic removes thesurface wax on the cotton fibers and aids in the degradation. On theother hand, the oxidizing agent tends to degrade the cellulosicmaterials but not the polyester contaminants. In addition, it has beenfound pursuant to the present invention that neither the hydroxide,oxidizing agent or their combination adversely affect the properties ofthe polyolefin being treated to any noticeable extent.

Typically, about one-half gallon to about 40 gallons, preferably about 1to about 20 gallons and most preferably about 2 to about 5 gallons ofthe aqueous composition of the hydroxide and oxidizing agent areemployed per pound of polyolefin being treated. For best results, thepolyolefin should be kept submerged in the aqueous composition employed.The polyolefin can be cut into smaller pieces for easier handling.

Typically, the treatment is carried out for about 10 minutes to about 3hours and more typically about 1/2 hour to about 2 hours at temperaturesof about 85° C. to about 150° C. The temperature employed should beequal to or below the boiling point of the solution. If necessary, theprocess can be carried out at higher temperatures, but under pressure.

If desired, the metals can be removed prior to or subsequent to thetreatment of the present invention by employing means known in the art.

It is further noted, that the hydroxide can be reused several timessince only small amounts of the hydroxide are depleted in any particulartreatment. On the other hand, the oxidizing agent is rapidly consumedduring the treatment.

The contaminants (i.e. cellulosic materials and polyesters) are degradedand removed from the polyolefin as soluble degradation products or fineparticles by draining and filtration. In addition, any by-productsformed from the hydroxide and oxidizing agents employed pursuant to thepresent invention are water soluble and accordingly can be diluted,neutralized, or destroyed, for safe disposal thereof, or recovered. Inaddition, the preferred hydroxide and oxidant, sodium hydroxide andsodium hypochlorite, respectively, are commercially available,relatively inexpensive, reasonably safe to handle, safe to mix and arewater soluble.

The following non-limiting examples are presented to further illustratethe present invention.

EXAMPLE 1

Into a glass, 4-liter stirred reaction vessel are added about 50 gramsof 11/2 inch cut polypropylene fibers contaminated with about gram ofcotton, about 1 gram of paper, and about 1 gram of polyester. About 1200milliliters of an aqueous solution of about 0.12% by weight of sodiumhypochlorite and about 20% by weight of sodium hydroxide are added tothe glass reaction vessel with stirring to cover the contaminatedpolypropylene. The temperature is heated to about 95° C. and thereaction is continued for about 2 hours. The polypropylene is separatedfrom the contaminants. All of the cotton, paper, and polyestercontaminants are degraded with the polypropylene remaining intact.

EXAMPLE 2

Example 1 is repeated except that the polypropylene is contaminated withabout 5 grams of polyester, 1 gram of cotton and 1 gram of paper. Theresults obtained are similar to those of Example 1 except that a fewmilligrams of polyester remained undegraded.

EXAMPLE 3

Example 1 is repeated except that the amount of treating solution isabout 600 milliliters. The results obtained are not as good as those inExample 1 in that most of the cotton and polyester is not degraded sincethe volume employed is not sufficient to adequately cover thepolypropylene during the process to affect the degradation. Increasingthe amount of treating solution to cover the polypropylene such as toabout 1200 milliters will result in degrading the remaining cotton andpolyester.

EXAMPLE 4

Example 1 is repeated except that the treating composition containsabout 0.12% by weight sodium hypochlorite and about 10% by weight sodiumhydroxide and the process is carried out for about 2 to 3 hours. Inaddition, 3 additional grams of polyester are added to the solution 1gram at a time during the process. All of the cotton, paper andpolyester are degraded with the polypropylene remaining intact.

EXAMPLE 5

Into a 2-liter glass reaction vessel are added about 25 grams of 11/2inch cut polypropylene fibers contaminated with about 0.5 grams ofcotton fibers, 0.5 grams of paper labels, and about 0.5 grams ofpolyester fibers. About 600 milliliters of an aqueous solution of about0.12 weight percent or sodium hypochlorite and about 30 weight percentof sodium hydroxide are added with vigorous agitation. The temperatureis increased to about 115° C. and the reaction is carried about forabout 25 minutes. The cotton, paper labels and polyester contaminantsare all degraded with the polypropylene remaining intact.

EXAMPLE 6

Example 5 is repeated except that the treating composition is an aqueoussolution containing about 15% by weight of sodium hydroxide and about0.12% by weight of sodium hypochlorite. The temperature employed isabout 108° C. and the reaction is carried out for about 45 to about 60minutes at which time all of the cotton, paper labels and polyester isdegraded. The polypropylene remains intact.

EXAMPLE 7

Example 5 is repeated except that the treating composition is an aqueoussolution containing about 20% by weight of sodium hydroxide and about0.12% by weight of sodium hypochlorite.nThe temperature employed isabout 110° C. and the reaction is carried out for about 35 minutes atwhich time all of the cotton, paper labels, and polyester contaminantsare degraded with the polypropylene remaining intact.

EXAMPLE 8

About 18 pounds of polypropylene contaminated with cotton, paper labelsand polyester fibers are introduced into a washer extractor machineavailable from Pellerin Laundry Machinery Sales Co. Also added are about61 gallons of a composition containing about 55 gallons of 20% sodiumhydroxide and about 1.54 gallons of a 4.73% aqueous solution of sodiumhypochlorite with the remainder being water introduced to the washer assteam. The contaminated polypropylene is agitated in the cleaningsolution for about 63 minutes at about 95° C. The cleaning solution isthen drained off from the polymer and about 61 gallons are collected ofwhich 55 gallons are saved for future use. All of the sodiumhypochlorite has been consumed and a minimum amount of cleaning solutionremains with the polymer. The polypropylene is then rinsed two timeswith about 120 gallons of cold water. About 16 pounds of recoveredpolypropylene is obtained.

EXAMPLE 9

Example 8 is repeated using as the 55 gallon sodium hydroxide portion,the 55 gallon cleaning solution saved from example 8 and 1.54 gallons of4.73% aqueous NaOCl solutions. The contaminated polypropylene isagitated in the cleaning solution for about 60 minutes at about 95° C.The cleaning solution is then drained from the polypropylene. Thepolypropylene is rinsed three times with 55 gallon batches of coldwater. All of the contaminants are degraded by the treatment.

The polypropylene recovered from this example is combined with thepolypropylene recovered from example 8 and then rinsed in about 120gallons of cold water containing about 1.5 liters of 20% aqueoussolution of a laundry sour neutralizer and particularly hydrofluosilicicacid followed by a second rinse in cold water. The sour neutralizer isemployed to neutralize the caustic content that might remain on thepoIypropylene fibers from the treatment. The above neutralizationsubstantially neutralizes the caustic but some still remains; thereforea somewhat higher concentration is to be used to assure completeneutralization.

EXAMPLE 10

Approximately 1 lb of woven and 1 lb of non-woven polypropylene balewrappers are cleaned in batches of approximately 50.0 g by the chemicalcleaning process described in Examples 1 through 9 and then combined. Novisible traces of cotton or polyester fibers are present. The 2-lbsample is manually cut into squares about 1"×1". The "squares" are notsuitable to feed to an extruder. The mixed samples are passed through aWiley mill to form a powdery mixture. Dry ice is added, along with the1" squares of polypropylene, to prevent fusion during the milling. Themilled product is baked in a convection oven (air) at 170° C. forapproximately 15 min during which time the fluffy, powdery mixture islightly fused. After vacuum drying for 24 h, the densified producteasily feeds to an extruder. Extrusion is performed using a 1"-screwextruder with a 250-mesh-screen pack. The extruded strand is cooled andpelletized. Microscopic examination shows no cotton or polyester fiberson the screen pack. No plugging is experienced. A melt-flow of 5.8dg/min (ASTM D1238) is exhibited by the cleaned, re-extruded product ascompared to the target range of 5-9 dg/min.

EXAMPLE 11

About 49 pounds of polypropylene fibers contaminated with cotton fibers,paper labels, and polyester fibers are introduced into a washerextractor machine available from Pellerin Laundry Machinery Sales Co.Into the machine are introduced about 61 gallons of a treating solutionconsisting of 55 gallons of the recovered solution from Example 9 andabout 1.54 gallons of an aqueous solution of 4.73% sodium hypochloritewith the remainder being water in the form of steam condensate. Thetemperature of the cleaning solution is maintained at about 95° C. forabout one hour. The polypropylene is recovered from the solution and isrinsed three times with 55 gallons of cold water. Since thepolypropylene is still contaminated, it is subjected to additionaltreatment with a cleaning solution of about 61 gallons consisting of 55gallons of the solution recycled from the above procedure and about 2.0gallons of the 4.73% aqueous solution of sodium hypochlorite. Themixture is agitated for about one hour at 95° C. The cleaning solutionis drained and extracted from the polypropylene. The polypropylene isrinsed once with 55 gallons of cold water containing about 1.5 liters of20% aqueous solution of laundry sour neutralizer (hydrofluosilicicacid). The polypropylene is then rinsed five more times with 55 gallonsof cold water and then rinsed twice with about 55 gallons of hot water.The polypropylene obtained is free from the contaminants and remainsintact in the treatment.

EXAMPLE 12

About 1,000 lb of polypropylene fibers contaminated with cotton fibers,paper labels, and polyester fibers, are cleaned in 30-lb batches using awasher/extractor machine available from Pellerin Laundry Machinery SalesCo. Into the machine are added about 56 gal of a treating solutionconsisting of 49 gal of an aqueous solution of 23% sodium hydroxide andabout 3,120 ml of an aqueous solution of 12.5% sodium hypochlorite withthe remainder being water in the form of steam condensate. Thetemperature of the cleaning solution is maintained at approximately 95°C. for one hour. The polypropylene is recovered from the solution and isrinsed two times with 56 gal of hot water and once with 56 gal of coldwater.

Cleaned polypropylene obtained by the above process is densified byheating to fusion temperature and then granulation. The densifiedpolypropylene is fed to an extruder at approximately 240° C. (avg barreltemp) and extruded through a screen pack or 30/200/100/30 screens. Themelt is extruded to a film, cut to strands, drawn to develop tensileproperties, and spooled for subsequent weaving tests N plugging of thescreen pack is observed in the runs made. Samples of the drawn fibersshowed a tenacity and melt-flow of 5.7 gm/den and 7 to 8 dg/min (ASTM D1238) as compared to a tenacity of 6 gm/den and a melt-flow index of 3.5to 4 dg/min, respectively, for the original polypropylene fiber.

What is claimed is:
 1. A process for treating polyolefin to removepolyester, and cellulosic contaminants therefrom which comprisescontacting polyolefin contaminated with polyester and cellulosiccontaminants with an oxidizing agent together with an aqueouscomposition of a hydroxide selected from the group consisting of alkalimetal hydroxide, alkaline earth metal hydroxide and mixtures thereof tothereby cause degradation of polyester and cellulosic contaminants. 2.The process of claim 1 wherein said cellulosic contaminants includecotton.
 3. The process of claim 1 wherein said cellulosic contaminantsinclude paper.
 4. The process of claim 1 wherein said oxidizing agent isemployed as an aqueous composition.
 5. The process of claim 1 whereinsaid oxidizing agent is present in said aqueous composition of ahydroxide.
 6. The process of claim 1 wherein said polyolefin iscontacted with an aqueous composition containing about 5 to about 50% byweight of said hydroxide and about 0.01% to about 10% by weight of saidoxidizing agent.
 7. The process of claim 6 wherein said hydroxideconsists essentially of sodium hydroxide and said oxidizing agentconsists essentially of sodium hypochlorite.
 8. The process of claim 6wherein said aqueous composition contains about 10 to about 30% byweight of said hydroxide and about 0.1 to about 1% by weight of saidoxidizing agent.
 9. The process of claim 3 wherein said hydroxideconsists essentially of sodium hydroxide and said oxidizing agentconsists essentially of sodium hypochlorite.
 10. The process of claim 6wherein said aqueous composition contains about 20% by weight of saidhydroxide, and about 0.1 to about 1% by weight of said oxidizing agent.11. The process of claim 10 wherein said hydroxide consists essentiallyof sodium hydroxide and said oxidizing agent consists essentially ofsodium hypochlorite.
 12. The process of claim 1 wherein about 1 gallonto about 40 gallons of said aqueous composition per pound of saidpolyolefin is employed.
 13. The process of claim 1 wherein about 1gallon to about 20 gallons of said aqueous composition per pound of saidpolyolefin is employed.
 14. The process of claim 1 wherein about 2gallons to about 5 gallons of aqueous composition per pound of saidpolyolefin is employed.
 15. The process of claim 1 which furtherincludes reducing the size of said polyolefin.
 16. The process of claim1 wherein the temperature is about 85° C. to 150° C.
 17. The process ofclaim 1 wherein said polyolefin is selected from the group consisting ofpolyethylene polypropylene, polyisobutylene, polystyrene polybutene-1and copolymers of monoolefins with each other.
 18. The process of claim1 which further includes forming fibers from the polyolefin after saidcontacting. .[.19. Fibers obtained by the process of claim 17..]..[.20.Recycled polyolefin obtained by the process of claim 1..].21. Theprocess of claim 1 which further includes separating the treatedpolyolefin from said aqueous composition and recycling said aqueouscomposition.
 22. The process of claim 1 which further includes formingmolded products from the resulting treated polyolefin.
 23. The processof claim 1 which further includes forming films from the resultingtreated polyolefin.
 24. The process of claim 8 wherein said aqueouscompositions contains about 0.12 to about 0.15% by weight of saidoxidizing agent.
 25. The process of claim 1 which comprises treatingsaid polyolefin simultaneously with separate compositions of saidoxidizing agent and said hydroxide.
 26. The process of claim 1 whereinsaid contacting is carried out in the absence of an organic solvent..Iadd.27. A process for treating polyolefin to remove cellulosiccontaminant therefrom which comprises contacting polyolefin contaminatedwith cellulosic contaminant with an oxidizing agent together with anaqueous composition of a hydroxide selected from the group consisting ofalkali metal hydroxide, alkaline earth metal hydroxide and mixturesthereof to thereby cause degradation of cellulosic contaminant..Iaddend..Iadd.28. The process of claim 27 wherein said cellulosiccontaminant includes cotton. .Iaddend..Iadd.29. The process of claim 27wherein said cellulosic contaminant includes paper. .Iaddend..Iadd.30.The process of claim 27 wherein said oxidizing agent is employed as anaqueous composition. .Iaddend..Iadd.31. The process of claim 27 whereinsaid oxidizing agent is present in said aqueous composition of ahydroxide. .Iaddend..Iadd.32. The process of claim 27 wherein saidpolyolefin is contacted with an aqueous composition containing about 5to about 50% by weight of said hydroxide and about 0.01% to about 10% byweight of said oxidizing agent. .Iaddend..Iadd.33. The process of claim32 wherein said hydroxide consists essentially of sodium hydroxide andsaid oxidizing agent consists essentially of sodium hypochlorite..Iaddend..Iadd.34. The process of claim 32 wherein said aqueouscomposition contains about 10 to about 30% by weight of said hydroxideand about 0.1 to about 1% by weight of said oxidizing agent..Iaddend..Iadd.35. The process of claim 34 wherein said hydroxideconsists essentially of sodium hydroxide and said oxidizing agentconsists essentially of sodium hypochlorite. .Iaddend..Iadd.36. Theprocess of claim 32 wherein said aqueous composition contains about 20%by weight of said hydroxide, and about 0.1 to about 1% by weight of saidoxidizing agent. .Iaddend..Iadd.37. The process of claim 36 wherein saidhydroxide consists essentially of sodium hydroxide and said oxidizingagent consists essentially of sodium hypochlorite. .Iaddend..Iadd.38.The process of claim 27 wherein about 1/2 gallon to about 40 gallons ofsaid aqueous composition per pound of said polyolefin is employed..Iaddend..Iadd.39. The process of claim 27 wherein about 1 gallon toabout 20 gallons of said aqueous composition per pound of saidpolyolefin is employed. .Iaddend..Iadd.40. The process of claim 27wherein about 2 gallons to about 5 gallons of aqueous composition perpound of said polyolefin is employed. .Iaddend..Iadd.41. The process ofclaim 27 wherein the temperature is about 85° C. to 150° C..Iaddend..Iadd.42. The process of claim 27 wherein said polyolefin isselected from the group consisting of polyethylene, polypropylene,polyisobutylene, polystyrene polybutene-1 and copolymers of monoolefinswith each other. .Iaddend..Iadd.43. The process of claim 27 whichfurther includes forming fibers from the polyolefin after saidcontacting. .Iaddend..Iadd.44. The process of claim 27 which furtherincludes forming molded products from the resulting treated polyolefin..Iaddend..Iadd.45. The process of claim 27 which further includesforming films from the resulting treated polyolefin. .Iaddend..Iadd.46.The process of claim 27 wherein said aqueous compositions contains about0.12 to about 0.15% by weight of said oxidizing agent..Iaddend..Iadd.47. The process of claim 27 which comprises treating saidpolyolefin simultaneously with separate compositions of said oxidizingagent and said hydroxide. .Iaddend..Iadd.48. The process of claim 27wherein said contacting is carried out in the absence of an organicsolvent. .Iaddend..Iadd.49. The process of claim 27 wherein saidpolyolefin is polypropylene. .Iaddend..Iadd.50. The process of claim 27wherein said polyolefin is polyethylene. .Iaddend.